US20030056806A1 - Method for cleaning damaged layers and polymer residue from semiconductor device - Google Patents
Method for cleaning damaged layers and polymer residue from semiconductor device Download PDFInfo
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- US20030056806A1 US20030056806A1 US09/955,126 US95512601A US2003056806A1 US 20030056806 A1 US20030056806 A1 US 20030056806A1 US 95512601 A US95512601 A US 95512601A US 2003056806 A1 US2003056806 A1 US 2003056806A1
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- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000004065 semiconductor Substances 0.000 title claims abstract description 49
- 238000004140 cleaning Methods 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims abstract description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000007598 dipping method Methods 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 45
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 43
- 230000015556 catabolic process Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011368 organic material Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3063—Electrolytic etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
- H01L21/67057—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing with the semiconductor substrates being dipped in baths or vessels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- C11D2111/22—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S438/00—Semiconductor device manufacturing: process
- Y10S438/906—Cleaning of wafer as interim step
Definitions
- the present invention is directed to a method of cleaning semiconductor devices and, more particularly, to a method of cleaning damaged layers and polymer residue on semiconductor devices.
- the contact region between layers decreases. Due to the small sizes involved, it is difficult to use conventional methods to form a contact region. Accordingly, a manufacturing process that self-aligns the contact pad with a semiconductor layer or an interconnect layer underlying the contact pad is employed for sub-quarter micron semiconductor devices.
- the resulting self-aligned contact has the advantages of allowing increased margin for misalignment error during photolithography, and reducing contact resistance. In the case of forming the SAC, an etch technique having high selectivity is necessary.
- a cleaning technique is required to remove the damage layer and polymer residue.
- a conventional cleaning solution contains APM (NH 4 OH/H 2 O 2 /H2O) or SPM (H 2 SO 4 /H 2 O 2 mixture).
- a method of cleaning a semiconductor device which includes the steps of: mixing HF and ozone water in a vessel to form a solution of HF and ozone water; and dipping a semiconductor device in the vessel containing the solution of HF and ozone water, wherein the solution contains about 0.034 to about 0.077 wt % HF.
- the ozone water contains about 5 to about 150 ppm ozone.
- the semiconductor device is dipped for about 1 to about 30 minutes.
- damaged layers and polymer residue are removed from the semiconductor device by the inventive method.
- a method of cleaning a semiconductor device including the steps of: mixing HF and ozone water in a vessel to form a solution of HF and ozone water; dipping a semiconductor device in the vessel containing the solution of HF and ozone water, and thereafter introducing ozone water into the vessel to replace the solution of HF and ozone water in the vessel, wherein the solution includes about 0.034 to about 0.077 wt % HF.
- ozone water is flowed into the vessel thereby causing an overflow of the solution of HF and ozone water out of the vessel.
- the ozone water is flowed into the vessel thereby causing the overflow of the solution of HF and ozone water out of the vessel for a period between about 1 and about 30 minutes.
- a method of cleaning a semiconductor device including the steps of: introducing HF and ozone water into a vessel to form a solution of HF and ozone water; mixing the HF and ozone water in the vessel to form a uniform solution of HF and ozone water; and dipping a semiconductor device in the vessel containing the uniform solution of HF and ozone water.
- the HF and ozone water are mixed to form a uniform solution by circulation, more specifically by means of a pump.
- the HF and ozone water are circulated by flowing the HF and ozone water from an inner bath to an outer bath and pumped back into the inner bath.
- a method of cleaning a semiconductor device including the steps of: introducing HF and ozone water into a vessel to form a solution of HF and ozone water; mixing the HF and ozone water in the vessel to form a uniform solution of HF and ozone water; dipping a semiconductor device in the vessel containing the uniform solution of HF and ozone water; and introducing ozone water into the vessel to replace the solution of HF and ozone water in the vessel.
- FIGS. 1A and 1B illustrate a cleaning method according to the present invention employing an exemplary apparatus as illustrated
- FIG. 2 is a graph showing the resistance of the contact region and breakdown voltage between the contact region and the conductive layer adjacent to the contact region as shown in FIGS. 5 and 6;
- FIGS. 3 and 4 are X-ray photospectroscopy (XPS) analysis graphs comparing cleaning methods according to the invention with prior art methods.
- FIGS. 5 and 6 illustrate examples of semiconductor processes in which embodiments of cleaning methods according to the present invention are applied.
- etch process After forming a contact hole, polymer residue and damage layers resulting from etch process, which are a kind of abnormal oxide, remain.
- the present invention use a cleaning solution with a mixture of ozone water and hydrofluoric acid (HF).
- Ozone water is effective in removing organic material such as polymers. Also, ozone water does not give rise to environment concerns.
- HF is effective in removing damage layers and polymer residue.
- Ozone decomposes to generate active radicals, which work as strong oxidizers.
- the decomposition mechanism is as follows:
- the active radicals react with the organic material on the surface of the semiconductor substrate to break C—H, C—C, and C ⁇ O bonds. Thus, organic material is easily removed and the surface is oxidized.
- reaction mechanism of ozone (O 3 ) is as follows:
- the present invention provides a cleaning process using the cleaning solution with ozone water and HF as follows (referring to FIGS. 1 A-B): first, inner bath 31 is supplied with ozone water and HF through supply lines 33 , 34 , respectively. Next, ozone water and HF are mixed by circulation. The circulation preferably is carried out by flowing the cleaning solution in the inner bath 31 into an outer bath 32 and then again flowing cleaning solution from outer bath 32 into the inner bath 31 through supply line 36 using a working pump connected to the outer bath 32 . Then, a semiconductor device is dipped into the bath.
- Ozone water is overflowed by supplying it through the supply line 33 .
- Overflowing ozone water rinses the cleaning solution off and makes the surface of the semiconductor device hydrophilic to prevent contamination on the surface of the semiconductor.
- step 1 in FIG. 1B it is effective that the concentration of the ozone water is between about 22 and about 27 ppm.
- FIG. 2 shows the resistance of the contact region and the breakdown voltage between the contact region and conductive layer adjacent to the contact region as shown in FIGS. 5 and 6, according to the concentration of HF after cleaning by using HF and ozone water solution (the concentration of O 3 in ozone water being about 20 ppm).
- Line D shows that as the concentration of HF increases, the resistance of the contact region decreases.
- the resistance below line B (line B indicating 40 kohm ) doesn't lead to failure of the device.
- the concentration of HF preferably should be more than about 0.034 wt %.
- Line C shows that the breakdown voltage between the contact region and the conductive layer adjacent to the contact region decreases as the concentration of HF increases.
- the decrease in the breakdown voltage means an increase in the leakage current between the contact region and the conductive layer.
- the breakdown voltage above line A ( line A indicating 18V) doesn't lead to failure of the device.
- the concentration of HF preferably should be less than about 0.077 wt %.
- the effective concentration of HF preferably is about 0.034 to about 0.077 wt % in order to decrease the resistance of the contact region without decreasing the breakdown voltage between the contact region and conductive layer.
- step 2 in FIG. 1B it is important to mix the ozone water and HF without dropping the concentration of O 3 .
- the ozone water and HF from the inner bath to the outer bath is circulated before dipping wafers into the bath. Without the circulation, the uniformity of etch rate is about 0.3%. With circulation, the uniformity of the etch rate is about 0.1 to about 0.15%.
- FIGS. 3 and 4 present X-ray Photospectroscopy (XPS) analysis graphs.
- the graph line 61 shows the result of no cleaning after forming a contact region.
- Graph line 62 shows the result of cleaning with EKC.
- Graph line 63 shows the result of cleaning with SMF.
- Graph line 64 shows the result of cleaning with ozone water and HF using a method of the present invention.
- FIG. 5 shows a Self Aligned Contact (SAC) structure, which is formed as follows.
- a gate insulator (not shown) is first formed on a semiconductor substrate 81 .
- a gate electrode 82 is formed on the gate insulator.
- a first dielectric layer 83 is then formed on the gate electrode 82 and the surface of the semiconductor substrate 81 .
- a second dielectric layer 84 is formed on the first dielectric layer 83 , wherein the second dielectric layer 84 has a high etch selectivity compared to first dielectric layer 83 .
- a contact hole 85 is formed by etching the second and first dielectric layers.
- the second dielectric layer 84 preferably has a high etch selectivity compared to the first dielectric layer 83 so that the gate electrode is not exposed during the etch.
- a nitride layer can be used as the first dielectric layer 83
- an oxide layer can be used as the second dielectric layer 84 .
- the damage layer and the polymer residue resulting from the etch process are removed.
- FIG. 6 shows a contact hole, wherein the contact hole connects a storage electrode to a contact pad.
- the contact hole is formed between bit lines.
- a dielectric layer 91 is provided in which a conductive layer 92 (i.e., a storage electrode) is formed.
- a bit line 93 is next formed, followed by formation of a first dielectric layer 94 and a second dielectric layer 95 .
- Contact hole 96 is then formed by etching the first and second dielectric layers 94 and 95 . After forming the contact hole 96 as shown FIG. 6, by using a cleaning method of the present invention, the damage layer and the polymer residue resulting from the etch process are removed.
Abstract
Description
- 1. Field of the Invention
- The present invention is directed to a method of cleaning semiconductor devices and, more particularly, to a method of cleaning damaged layers and polymer residue on semiconductor devices.
- 2. Description of the Related Art
- As the design rule of semiconductor device gets smaller, the contact region between layers decreases. Due to the small sizes involved, it is difficult to use conventional methods to form a contact region. Accordingly, a manufacturing process that self-aligns the contact pad with a semiconductor layer or an interconnect layer underlying the contact pad is employed for sub-quarter micron semiconductor devices. The resulting self-aligned contact (SAC) has the advantages of allowing increased margin for misalignment error during photolithography, and reducing contact resistance. In the case of forming the SAC, an etch technique having high selectivity is necessary.
- However, it is difficult to remove the damage layer and polymer residue resulting from high-selectivity etch. Accordingly, a cleaning technique is required to remove the damage layer and polymer residue. A conventional cleaning solution contains APM (NH4OH/H2O2/H2O) or SPM (H2SO4/H2O2 mixture).
- Metal layers are often used in order to increase the speed of semiconductor devices. However, conventional cleaning solutions such, as the foregoing solution, damage metal layers. Therefore, cleaning solutions with EKC (NH4OH/C6H4(OH)2/Aminoethoxyethanol) or SMF ( NH4OH/CH3COOH/H2O/HF) are used. However, EKC and SMF solutions do not remove the damage layer and polymer residue resulting from etch processes;
- therefore, contact resistance increases and failures of semiconductor devices occur. Accordingly, there is a need for a method for removing the damaged layer and polymer residue without damaging the metal layer of a semiconductor device.
- In accordance with one aspect of the present invention, there is provided a method of cleaning a semiconductor device which includes the steps of: mixing HF and ozone water in a vessel to form a solution of HF and ozone water; and dipping a semiconductor device in the vessel containing the solution of HF and ozone water, wherein the solution contains about 0.034 to about 0.077 wt % HF.
- In a more specific embodiment, the ozone water contains about 5 to about 150 ppm ozone. In another more specific embodiment, the semiconductor device is dipped for about 1 to about 30 minutes.
- Preferably, damaged layers and polymer residue are removed from the semiconductor device by the inventive method.
- In accordance with another aspect of the present invention, there is provided a method of cleaning a semiconductor device including the steps of: mixing HF and ozone water in a vessel to form a solution of HF and ozone water; dipping a semiconductor device in the vessel containing the solution of HF and ozone water, and thereafter introducing ozone water into the vessel to replace the solution of HF and ozone water in the vessel, wherein the solution includes about 0.034 to about 0.077 wt % HF.
- In more specific embodiments, ozone water is flowed into the vessel thereby causing an overflow of the solution of HF and ozone water out of the vessel. According to specific embodiments, the ozone water is flowed into the vessel thereby causing the overflow of the solution of HF and ozone water out of the vessel for a period between about 1 and about 30 minutes.
- In accordance with a further aspect of the present invention, there is provided a method of cleaning a semiconductor device including the steps of: introducing HF and ozone water into a vessel to form a solution of HF and ozone water; mixing the HF and ozone water in the vessel to form a uniform solution of HF and ozone water; and dipping a semiconductor device in the vessel containing the uniform solution of HF and ozone water.
- In more particular embodiments, the HF and ozone water are mixed to form a uniform solution by circulation, more specifically by means of a pump.
- In specific embodiments, the HF and ozone water are circulated by flowing the HF and ozone water from an inner bath to an outer bath and pumped back into the inner bath.
- In accordance with still another aspect of the present invention, there is provided a method of cleaning a semiconductor device including the steps of: introducing HF and ozone water into a vessel to form a solution of HF and ozone water; mixing the HF and ozone water in the vessel to form a uniform solution of HF and ozone water; dipping a semiconductor device in the vessel containing the uniform solution of HF and ozone water; and introducing ozone water into the vessel to replace the solution of HF and ozone water in the vessel.
- Other features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. It is to be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the present invention, are given by way of illustration and not limitation. Many changes and modifications within the scope of the present invention may be made without departing from the spirit thereof, and the invention includes all such modifications.
- The above features and advantages of the present invention will become more apparent by describing in detail specific embodiments thereof with reference to the attached drawings in which:
- FIGS. 1A and 1B illustrate a cleaning method according to the present invention employing an exemplary apparatus as illustrated;
- FIG. 2 is a graph showing the resistance of the contact region and breakdown voltage between the contact region and the conductive layer adjacent to the contact region as shown in FIGS. 5 and 6;
- FIGS. 3 and 4 are X-ray photospectroscopy (XPS) analysis graphs comparing cleaning methods according to the invention with prior art methods; and
- FIGS. 5 and 6 illustrate examples of semiconductor processes in which embodiments of cleaning methods according to the present invention are applied.
- The priority Korean Patent Application No. 00-xxxxx, filed xxxxx, 2000, is hereby incorporated in its entirety by reference.
- After forming a contact hole, polymer residue and damage layers resulting from etch process, which are a kind of abnormal oxide, remain. In order to remove the polymer residue and damage layers, the present invention use a cleaning solution with a mixture of ozone water and hydrofluoric acid (HF). Ozone water is effective in removing organic material such as polymers. Also, ozone water does not give rise to environment concerns. HF is effective in removing damage layers and polymer residue.
- Ozone decomposes to generate active radicals, which work as strong oxidizers. The decomposition mechanism is as follows:
- O3+OH−→O2 −+HO2* (1)
- O3+HO2*→2O2+OH* (2)
- O3+OH*→O2+HO2* (3)
- 2H2O*→O3+H2O (4)
- HO2*+OH*→O2+H2O (5)
- The active radicals react with the organic material on the surface of the semiconductor substrate to break C—H, C—C, and C═O bonds. Thus, organic material is easily removed and the surface is oxidized.
- The reaction mechanism of ozone (O3) is as follows:
- O3+organic material (e.g. polymer)→CO2+H2O (1)
- O3+M(surface)→MOx+O2 (2)
- The present invention provides a cleaning process using the cleaning solution with ozone water and HF as follows (referring to FIGS.1A-B): first,
inner bath 31 is supplied with ozone water and HF throughsupply lines inner bath 31 into anouter bath 32 and then again flowing cleaning solution fromouter bath 32 into theinner bath 31 throughsupply line 36 using a working pump connected to theouter bath 32. Then, a semiconductor device is dipped into the bath. - It is desirable to overflow the ozone water after the last step (3) in FIG. 1B. Ozone water is overflowed by supplying it through the
supply line 33. Overflowing ozone water rinses the cleaning solution off and makes the surface of the semiconductor device hydrophilic to prevent contamination on the surface of the semiconductor. - In
step 1 in FIG. 1B, it is effective that the concentration of the ozone water is between about 22 and about 27 ppm. - FIG. 2 shows the resistance of the contact region and the breakdown voltage between the contact region and conductive layer adjacent to the contact region as shown in FIGS. 5 and 6, according to the concentration of HF after cleaning by using HF and ozone water solution (the concentration of O3 in ozone water being about 20 ppm). Line D shows that as the concentration of HF increases, the resistance of the contact region decreases. The resistance below line B (line B indicating 40 kohm ) doesn't lead to failure of the device. To meet this condition, the concentration of HF preferably should be more than about 0.034 wt %.
- Line C shows that the breakdown voltage between the contact region and the conductive layer adjacent to the contact region decreases as the concentration of HF increases. The decrease in the breakdown voltage means an increase in the leakage current between the contact region and the conductive layer. The breakdown voltage above line A ( line A indicating 18V) doesn't lead to failure of the device. To meet this condition, the concentration of HF preferably should be less than about 0.077 wt %.
- Accordingly, the effective concentration of HF preferably is about 0.034 to about 0.077 wt % in order to decrease the resistance of the contact region without decreasing the breakdown voltage between the contact region and conductive layer.
- In
step 2 in FIG. 1B, it is important to mix the ozone water and HF without dropping the concentration of O3. After supplying the ozone water and HF into the inner bath, the ozone water and HF from the inner bath to the outer bath is circulated before dipping wafers into the bath. Without the circulation, the uniformity of etch rate is about 0.3%. With circulation, the uniformity of the etch rate is about 0.1 to about 0.15%. Referring to table 1, it is desirable that the circulation proceed for about 30 to about 60 secs after supplying the ozone water and HF.TABLE 1 Circulation 0 30 60 120 time(sec.) Drop of O3 1.3 ppm 2.2 ppm 4.7 ppm concentration Etch About 0.3% 0.1˜0.15% 0.1˜0.15% 0.1˜0.15% uniformity - FIGS. 3 and 4 present X-ray Photospectroscopy (XPS) analysis graphs. The
graph line 61 shows the result of no cleaning after forming a contact region.Graph line 62 shows the result of cleaning with EKC.Graph line 63 shows the result of cleaning with SMF.Graph line 64 shows the result of cleaning with ozone water and HF using a method of the present invention. - As seen in FIG. 3, when the present invention is applied to cleaning the contact region, the SiOx peak decreased. SiOx is considered a contaminant. As seen in FIG. 4, when the present invention is applied to cleaning the contact region, the Si—C peak decreases.
- FIGS. 5 and 6 show examples of semiconductor processes in which methods according to the present invention is applied. FIG. 5 shows a Self Aligned Contact (SAC) structure, which is formed as follows. A gate insulator (not shown) is first formed on a
semiconductor substrate 81. Next, agate electrode 82 is formed on the gate insulator. Afirst dielectric layer 83 is then formed on thegate electrode 82 and the surface of thesemiconductor substrate 81. Asecond dielectric layer 84 is formed on thefirst dielectric layer 83, wherein thesecond dielectric layer 84 has a high etch selectivity compared tofirst dielectric layer 83. Then, acontact hole 85 is formed by etching the second and first dielectric layers. - The
second dielectric layer 84 preferably has a high etch selectivity compared to thefirst dielectric layer 83 so that the gate electrode is not exposed during the etch. For example, a nitride layer can be used as thefirst dielectric layer 83, and an oxide layer can be used as thesecond dielectric layer 84. - After forming the contact hole by using a cleaning method according to the present invention, the damage layer and the polymer residue resulting from the etch process are removed.
- FIG. 6 shows a contact hole, wherein the contact hole connects a storage electrode to a contact pad. The contact hole is formed between bit lines. Thus, a
dielectric layer 91 is provided in which a conductive layer 92 (i.e., a storage electrode) is formed. Abit line 93 is next formed, followed by formation of afirst dielectric layer 94 and asecond dielectric layer 95.Contact hole 96 is then formed by etching the first and second dielectric layers 94 and 95. After forming thecontact hole 96 as shown FIG. 6, by using a cleaning method of the present invention, the damage layer and the polymer residue resulting from the etch process are removed. - While this invention has been particularly shown and described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made to the described embodiments without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (42)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US09/955,126 US6802911B2 (en) | 2001-09-19 | 2001-09-19 | Method for cleaning damaged layers and polymer residue from semiconductor device |
KR10-2001-0076559A KR100425475B1 (en) | 2001-09-19 | 2001-12-05 | Method for cleaning damage layers and polymer residue from semiconductor device |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US09/955,126 US6802911B2 (en) | 2001-09-19 | 2001-09-19 | Method for cleaning damaged layers and polymer residue from semiconductor device |
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US20030056806A1 true US20030056806A1 (en) | 2003-03-27 |
US6802911B2 US6802911B2 (en) | 2004-10-12 |
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US09/955,126 Expired - Lifetime US6802911B2 (en) | 2001-09-19 | 2001-09-19 | Method for cleaning damaged layers and polymer residue from semiconductor device |
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US20030127425A1 (en) * | 2002-01-07 | 2003-07-10 | Hirohiko Nishiki | System and method for etching resin with an ozone wet etching process |
US20050130420A1 (en) * | 2003-12-10 | 2005-06-16 | Huang Chih Y. | Cleaning method using ozone DI process |
US20060093968A1 (en) * | 2004-11-04 | 2006-05-04 | Nec Lcd Technologies, Ltd | Method of processing substrate and chemical used in the same |
CN110364424A (en) * | 2019-07-29 | 2019-10-22 | 中微半导体设备(上海)股份有限公司 | The cleaning method of semiconductor processing equipment components |
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US20030127425A1 (en) * | 2002-01-07 | 2003-07-10 | Hirohiko Nishiki | System and method for etching resin with an ozone wet etching process |
US20050130420A1 (en) * | 2003-12-10 | 2005-06-16 | Huang Chih Y. | Cleaning method using ozone DI process |
US20060093968A1 (en) * | 2004-11-04 | 2006-05-04 | Nec Lcd Technologies, Ltd | Method of processing substrate and chemical used in the same |
CN100383913C (en) * | 2004-11-04 | 2008-04-23 | Nec液晶技术株式会社 | Method of processing substrate and chemical used in the same |
CN110364424A (en) * | 2019-07-29 | 2019-10-22 | 中微半导体设备(上海)股份有限公司 | The cleaning method of semiconductor processing equipment components |
Also Published As
Publication number | Publication date |
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KR20030025155A (en) | 2003-03-28 |
US6802911B2 (en) | 2004-10-12 |
KR100425475B1 (en) | 2004-03-30 |
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